Microscale Metal Patterning on Any Substrate: Exploring the Potential of Poly(dopamine) Films in High Resolution, High Contrast, Conformal Lithography.

We have explored the potential of poly(dopamine) (PDA) thin films as versatile, high resolution conformal photoresists, using catalytic photoreduction of silver ions to micropattern the film. The combination of photosensitivity, biocompatibilty, and straightforward deposition under mild conditions into thin (∼45 nm) conformal coatings on nearly any material makes PDA films of interest in lithographic patterning on highly nonplanar geometries as well as on soft and biological materials where standard photoresists cannot be used. PDA and poly(norepinephrine) (PNE) films deposited with a standard autoxidation process were investigated along with PDA film deposited with a fast oxidation (FO) technique.

Interferometric spectroscopy and high-speed orientation detection of individual gold nanorods.

Although 3D positional tracking of single nanoparticles in suspension is now an established technique, the small size of the particles compared to the wavelength of light has meant it is still challenging to optically characterize individual diffusing particles in other ways. Here we introduce Quantitative Optical Anisotropy Imaging (QOAI), an interferometric technique that fills some of this gap by allowing for real-time tracking of orientation as well as spectroscopic characterization of polarizability in nanoparticles at the microsecond timescale. Applying this to gold nanorods, we demonstrate measurement of nanorod orientation with high precision with simultaneous spectroscopic characterization of the rods' longitudinal plasmon resonance.

Tunable gap plasmons in gold nanospheres adsorbed into a pH-responsive polymer film.

Hypothesis: Plasmon nanorulers are exquisitely sensitive distance sensors that are based on the electromagnetic interaction between metal nanoparticles and surfaces. We hypothesize that nanorulers can act as quantitative probes of processes such as particle aggregation and adsorption, and deploy them to investigate particle adsorption onto stimulus-responsive polymer films. While such systems have previously been qualitatively investigated with plasmon nanorulers, our quantitative analysis should provide deeper insights.

Multi-photon patterning of photoactive o-nitrobenzyl ligands bound to gold surfaces.

We quantitatively investigate lithographic patterning of a thiol-anchored self-assembled monolayer (SAM) of photocleavable o-nitrobenzyl ligands on gold through a multi-photon absorption process at 1.7 eV (730 nm wavelength). The photocleaving rate increases faster than the square of the incident light intensity, indicating a process more complex than simple two-photon absorption.

Light-Directed Patchy Particle Fabrication and Assembly from Isotropic Silver Nanoparticles.

We demonstrate the creation of anisotropic patchy silver nanospheroids (AgNSs) using linearly polarized UV light and a photo-uncaging o-nitrobenzyl-based ligand, which anchors to the AgNSs by two gold-sulfur bonds. Exposure to a 1 J/cm dose of UV light induces a photo-uncaging reaction in the ligand that reveals a primary amine on the surface. By using linearly polarized UV light, we meter the exposure dose such that only the poles of the nanoparticle receive a full dose, limiting the photo-uncaging reaction primarily to the particle's plasmonic hot spots.

Fluorescence lifetime based characterization of active and tunable plasmonic nanostructures.

We report a non-contact method that utilizes fluorescence lifetime (FL) to characterize morphological changes of a tunable plasmonic nanostructure with nanoscale accuracy. The key component of the plasmonic nanostructure is pH-responsive polyelectrolyte multilayers (PEMs), which serve as a dynamically tunable "spacer" layer that separates the plasmonic structure and the fluorescent materials. The validity of our method is confirmed through direct comparison with ellipsometry and atomic force microscopy (AFM) measurements.

Impact of lithography on the fluorescence dynamics of self-assembled fluorophores.

Micro- and nano-patterned fluorescent materials are important for many photonic devices and applications. In this paper, we investigate the impact of three common lithographical techniques, deposition and removal of sacrificial masks, ultraviolet ablation, and focused ion beam milling, on self-assembled fluorophores. We find that different patterning techniques can dramatically change the fluorescence lifetime of the fluorophores and that the degree of modification depends on the patterning techniques.

High quality factor silica microspheres functionalized with self-assembled nanomaterials.

With extremely low material absorption and exceptional surface smoothness, silica-based optical resonators can achieve extremely high cavity quality (Q) factors. However, the intrinsic material limitations of silica (e.g.

Two-photon activated two-photon fluorescence and binding of azidocoumarin in a gelatin matrix.

We study the creation of fluorescence patterns inside a gelatin gel by way of two-photon photoactivation of 7-azido-4-trifluoromethyl-1,2-benzopyrone (azidocomarin 151) contained in the gel matrix. As ultrafast light pulses are focused into the gel, onset of two-photon fluorescence, highly nonlinear in the applied optical power, is observed as azidocoumarin is converted into a fluorescent dye that binds to the gelatin. We fit the time dependence of the fluorescence to a model that incorporates the competition between coumarin photoactivation and photobleaching as well as the gradual degradation of the gel when it is exposed to the high intensity laser light.

Irreversible adsorption of gold nanospheres on fiber optical tapers and microspheres.

We study the adsorption of gold nanospheres onto cylindrical and spherical glass surfaces from quiescent particle suspensions. The surfaces consist of tapers and microspheres fabricated from optical fibers and were coated with a polycation, enabling irreversible nanosphere adsorption. Our results fit well with theory, which predicts that particle adsorption rates depend strongly on surface geometry and can exceed the planar surface deposition rate by over two orders of magnitude when particle diffusion length is large compared to surface curvature.

Amine-rich polyelectrolyte multilayers for patterned surface fixation of nanostructures.

We describe a lithographic method for directly patterning the adhesive properties of amine-rich layer-by-layer assembled polymer films, useful for positioning metal and other nanostructures. The adhesive properties of the films are sufficiently robust that the films can be patterned with standard as opposed to soft lithographic methods. We perform the patterning with a lithographically defined evaporated aluminum mask which protects selected regions of the substrate, passivating adhesion in the exposed regions with acetic anhydride.

Restricted meniscus convective self-assembly.

Convective (or evaporation-induced) self-assembly is a standard technique for depositing uniform, poly-crystalline coatings of nanospheres across multiple square centimeters on the timescale of minutes. In this paper, we present a variation of this technique, where the drying meniscus is restricted by a straight-edge located approximately 100 microm above the substrate adjacent to the drying zone. Surprisingly, we find this technique to yield films at roughly twice the growth rate compared to the standard technique.

Plasmon-enhanced second-harmonic generation from ionic self-assembled multilayer films.

We have demonstrated large enhancements of the effective second-order nonlinear susceptibility (chi(2)) of ionic self-assembled multilayer (ISAM) films, causing a film with just 3 bilayers to be optically equivalent to a 700-1000 bilayer film. This was accomplished by using nanosphere lithography to deposit silver nanoparticles on the ISAM film, tuning the geometry of the particles to make their plasmonic resonances overlap the frequency of optical excitation. An enhancement in the efficiency of second harmonic generation (SHG) by as much as 1600 times was observed.